JP2009041009A5 - - Google Patents
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- JP2009041009A5 JP2009041009A5 JP2008186846A JP2008186846A JP2009041009A5 JP 2009041009 A5 JP2009041009 A5 JP 2009041009A5 JP 2008186846 A JP2008186846 A JP 2008186846A JP 2008186846 A JP2008186846 A JP 2008186846A JP 2009041009 A5 JP2009041009 A5 JP 2009041009A5
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すなわち、本発明は、
(1)芳香族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、芳香族ジカルボニル単位(R)および3官能の芳香族有機残基(B)を含み、芳香 族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、およ び、芳香族ジカルボニル単位(R)が、それぞれ下式(3)で表される構造単位から選ばれる少なくとも1種の構造単位であり、かつ、上記P、Q、R、およびBの含有量の合計に対してBの含有量が7.5〜50モル%の範囲にあり、構造単位P、QおよびRの平均 モル含有量をそれぞれp、qおよびrとしたときに、p/qが5/95以上、かつ、p/ rが5/95以上であり、末端のカルボン酸基量が1×10-4当量/g以下であることを特徴とする溶融液晶性を示す樹状ポリエステル、
(2)芳香族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、芳香族ジカルボニル単位(R)および3官能の芳香族有機残基(B)を含み、芳香 族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、およ び、芳香族ジカルボニル単位(R)が、それぞれ上式(3)で表される構造単位から選ばれる少なくとも1種の構造単位であり、かつ、上記P、Q、R、およびBの含有量の合計に対してBの含有量が7.5〜50モル%の範囲にあり、構造単位P、QおよびRの平均 モル含有量をそれぞれp、qおよびrとしたときに、p/qが5/95以上、かつ、p/ rが5/95以上であり、さらにカルボン酸反応性単官能化合物残基を含有することを特徴とする(1)に記載の樹状ポリエステル、
(3)前記カルボン酸反応性単官能化合物が、オルトエステル、エポキシド、オキサゾリ ン、イソシアネートから選ばれる少なくとも1種の化合物である(2)に記載の樹状ポリエステル、
(4)前記オキサゾリン化合物が、下式(1)で表される化合物である(3)に記載の樹状ポリエステル、
That is, the present invention
(1) an aromatic oxycarbonyl units (P), includes aromatic and / or aliphatic dioxy units (Q), Fang aromatic dicarboxylic sulfonyl unit (R) and trifunctional aromatic organic residue (B), an aromatic family oxycarbonyl units (P), aromatic and / or aliphatic dioxy units (Q), and aromatic dicarbonyl units (R) is selected from structural units represented by the following formula (3), respectively at least one structural unit, and the P, Q, there R, and the content of B with respect to the total content of the B is in the range of 7.5 to 50 mol%, structural units P, Q and the average molar content of each p of R, when the q and r, p / q is 5/95 or more and is a p / r is 5/95 or more, a carboxylic acid group content of terminal 1 × 10-4 shows a liquid crystalline, wherein the equivalent weight / g or less Dendritic polyester,
(2) aromatic oxycarbonyl units (P), includes aromatic and / or aliphatic dioxy units (Q), Fang aromatic dicarboxylic sulfonyl unit (R) and trifunctional aromatic organic residue (B), an aromatic family oxycarbonyl units (P), aromatic and / or aliphatic dioxy units (Q), and aromatic dicarbonyl units (R) is selected from structural units represented by the respective on formula (3) at least one structural unit, and the P, Q, there R, and the content of B with respect to the total content of the B is in the range of 7.5 to 50 mol%, structural units P, Q P / q is 5/95 or more and p / r is 5/95 or more when the average molar content of R and R is p, q and r, respectively. The tree according to (1), comprising a group Polyester,
(3) The carboxylic acid-reactive monofunctional compounds, ortho ester, epoxide, oxazoline down, dendritic polyesters according to at least one compound selected from isocyanate (2),
(4) The dendritic polyester according to (3), wherein the oxazoline compound is a compound represented by the following formula (1):
(ここで、Rは炭素数4以下のアルキル基、炭素数4以下のアルキルカルボニル基、フェニル基およびベンゾイル基から選ばれるいずれかである) (Here, R is any one selected from an alkyl group having 4 or less carbon atoms, an alkylcarbonyl group having 4 or less carbon atoms, a phenyl group, and a benzoyl group )
(6)式(4)で示される基本骨格を有する(1)〜(5)のいずれかに記載の樹状ポリエステル、( 6 ) Dendritic polyester in any one of (1)-( 5 ) which has the basic skeleton shown by Formula (4),
(ここで、Bは3官能化合物の残基であり、B−B間は上式(3)で表される構造単位を介して、もしくはエステル結合および/またはアミド結合により直接、結合している)
(7)樹状ポリエステルの数平均分子量が1000〜5000である(1)〜(6)のいずれかに記載の樹状ポリエステル、
(8)(1)〜(7)のいずれかに記載の樹状ポリエステルを熱可塑性樹脂に配合してなる熱可塑性樹脂組成物、
(9)熱可塑性樹脂100重量部に対して樹状ポリエステル0.01〜99重量部を含む(8)に記載の熱可塑性樹脂組成物、
(10)下式R1で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、下式R2で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、下式R3で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、および3官能以上の多官能単量体から得られる含む樹状ポリエステルと、カルボン酸反応性単官能化合物、および熱可塑性樹脂とを二軸押出機で混練する(8)または(9)のいずれかに記載の熱可塑性樹脂組成物の製造方法、(Here, B is a residue of a trifunctional compound, and BB is directly bonded via the structural unit represented by the above formula (3) or by an ester bond and / or an amide bond. )
( 7 ) The dendritic polyester according to any one of (1) to ( 6 ), wherein the dendritic polyester has a number average molecular weight of 1,000 to 5,000.
( 8 ) A thermoplastic resin composition obtained by blending the dendritic polyester according to any one of (1) to ( 7 ) with a thermoplastic resin,
( 9 ) The thermoplastic resin composition according to ( 8 ), comprising 0.01 to 99 parts by weight of a dendritic polyester with respect to 100 parts by weight of the thermoplastic resin,
( 10 ) A monomer containing at least one structural unit selected from the structural units represented by the following formula R1, and a monomer containing at least one structural unit selected from the structural units represented by the following formula R2. , A monomer containing at least one structural unit selected from structural units represented by the following formula R3, and a dendritic polyester obtained from a trifunctional or higher polyfunctional monomer, and a carboxylic acid-reactive monofunctional ( 8 ) or the method for producing a thermoplastic resin composition according to any one of ( 9 ), wherein the compound and the thermoplastic resin are kneaded with a twin-screw extruder,
(ただし、式中Yは、水素原子、ハロゲン原子およびアルキル基から選ばれる少なくとも1種である。式中nは2〜8の整数である)
(11)(8)または(9)のいずれかに記載の熱可塑性樹脂組成物からなる成形品、
(12)上式R1で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、上式R2で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、上式R3で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体、および3官能以上の多官能単量体を反応させた後、末端にカルボン酸反応性単官能化合物を反応させる樹状ポリエステルの製造方法であって、該多官能化合物の添加量(モル)が、R1、R2、およびR3で表される構造単位から選ばれる少なくとも1種の構造単位を含む単量体および多官能単量体の合計に対して7.5モル%以上である樹状ポリエステルの製造方法、
(13)前記カルボン酸反応性単官能化合物が、オルトエステル、エポキシド、オキサゾ リン、およびイソシアネートから選ばれる少なくとも1種の化合物である(12)に記載の樹状ポリエステルの製造方法、
(14)前記オキサゾリン化合物が、下式(5)で表される化合物である(13)に記載の樹状ポリエステルの製造方法、(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8)
( 11 ) A molded article comprising the thermoplastic resin composition according to any one of ( 8 ) and ( 9 ),
( 12 ) A monomer containing at least one structural unit selected from structural units represented by the above formula R1, and a monomer containing at least one structural unit selected from structural units represented by the above formula R2. After reacting a monomer containing at least one structural unit selected from the structural units represented by the above formula R3, and a polyfunctional monomer having three or more functional groups, the terminal is a carboxylic acid-reactive monofunctional compound Wherein the addition amount (mol) of the polyfunctional compound comprises at least one structural unit selected from structural units represented by R1, R2, and R3. A method for producing a dendritic polyester that is 7.5 mol% or more based on the total of the body and the polyfunctional monomer,
(13) The carboxylic acid-reactive monofunctional compounds, ortho ester, epoxide, oxazoline phosphorus, and a method of producing dendritic polyesters according to at least one compound selected from the isocyanate (12),
( 14 ) The method for producing a dendritic polyester according to ( 13 ), wherein the oxazoline compound is a compound represented by the following formula ( 5 ):
(ここで、Rは炭素数4以下のアルキル基およびフェニル基から選ばれるいずれかである。)
(15)前記エポキシド化合物が、下式(6)で表される化合物である(13)に記載の樹状ポリエステルの製造方法、(Here, R is any one selected from an alkyl group having 4 or less carbon atoms and a phenyl group.)
( 15 ) The method for producing a dendritic polyester according to ( 13 ), wherein the epoxide compound is a compound represented by the following formula ( 6 ):
本発明の樹状ポリエステルは、芳香族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、および、芳香族ジカルボニル単位(R)から選ばれる少なくとも1種の構造単位と3官能の有機残基(B)とを含み、かつ、上記P、Q、RおよびBの含有量の合計に対してBの含有量が7.5〜50モル%の範囲にあり、末端のカルボン酸基量が1×10-4当量/g以下である樹状ポリエステルである。Dendritic polyesters of the present invention, an aromatic oxycarbonyl units (P), aromatic and / or aliphatic dioxy units (Q), and, at least one structural unit selected from aromatic dicarboxylic sulfonyl units (R) A trifunctional organic residue (B), and the content of B is in the range of 7.5 to 50 mol% with respect to the total content of P, Q, R and B, weight carboxylic acid group is a dendritic polyester or less 1 × 10 -4 eq / g.
ここで、芳香族オキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、および、芳香族ジカルボニル単位(R)は、それぞれ下式(7)で表される構造単位であることが好ましい。Here, an aromatic oxycarbonyl units (P), aromatic and / or aliphatic dioxy units (Q), and an aromatic dicarboxylic sulfonyl unit (R) is a structural unit represented by the following formula (7), respectively Preferably there is.
分子末端に存在するカルボン酸基量の定量は、中和滴定法によって行うことができる。例えば、樹状ポリエステル0.5gをo−クロロフェノールまたはo−クレゾール10mLに90℃に加熱しながら溶解させ、冷却した後、クロロホルム4mLを加える。ブロモフェノールブルー−エタノール溶液(0.2重量%)を数滴加えた後、滴定試薬(0.04M水酸化カリウム−メタノール溶液)をビュレットを用いて滴下し、中和点に達するまでに滴下した滴定試薬量から樹状ポリエステルの末端カルボン酸基量を計算できる。The amount of the carboxylic acid group present at the molecular end can be determined by neutralization titration. For example, 0.5 g of dendritic polyester is dissolved in 10 mL of o-chlorophenol or o-cresol while heating at 90 ° C., cooled, and then 4 mL of chloroform is added. After adding a few drops of bromophenol blue-ethanol solution (0.2 wt%), a titration reagent (0.04M potassium hydroxide-methanol solution) was added dropwise using a burette and added until the neutralization point was reached. It can be calculated terminal carboxylic acid group amount of dendritic polyester from titrant volume.
また、樹状ポリエステルの芳香族ヒドロキシカルボニル単位(P)、芳香族および/または脂肪族ジオキシ単位(Q)、芳香族ジカルボニル単位(R)は、樹状ポリエステルの分岐間の枝構造部分を構成する単位である。p、qおよびrはそれぞれ構造単位P、QおよびRの平均含有量(モル比)であり、このp、qおよびrの値は、例えば、樹状ポリエステルをペンタフルオロフェノール50重量%:重クロロホルム50重量%の混合溶媒に溶解し、40℃でプロトン核の核磁気共鳴スペクトル分析を行い、それぞれの構造単位に由来するピーク強度比から求めることができる。各構造単位のピーク面積強度比から、平均含有率を算出し、小数点3桁は四捨五入する。Further, the aromatic hydroxy carbonyl units of dendritic polyester (P), aromatic and / or aliphatic dioxy units (Q), aromatic dicarboxylic sulfonyl unit (R) is configured to branch structure portion between the branch of the dendritic polyester Unit. p, q, and r are average contents (molar ratio) of the structural units P, Q, and R, respectively. The values of p, q, and r are, for example, 50% by weight of pentafluorophenol: heavy chloroform It can melt | dissolve in a 50 weight% mixed solvent, can perform the nuclear magnetic resonance spectrum analysis of a proton nucleus at 40 degreeC, and can obtain | require from the peak intensity ratio derived from each structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off.
分子量を上げるためには、トリメシン酸のカルボン酸基量に相当する分だけ、ハイドロキノンや4,4’−ジヒドロキシビフェニルなどのジヒドロキシモノマーを、ジカルボン酸モノマーに対して過剰に加え、全単量体におけるカルボン酸と水酸基当量を合わせることが好ましい。To increase the molecular weight, the amount corresponding to the carboxylic acid group amount of trimesic acid, a dihydroxy monomer such as hydroquinone or 4,4'-dihydroxybiphenyl, excess added to dicarboxylic acid monomer, the total monomer The carboxylic acid and the hydroxyl equivalent are preferably combined.
また、得られた樹状ポリエステル(A−1)の分子末端カルボン酸基量は、3.0×10−5当量/gであった。Moreover, the amount of molecular terminal carboxylic acid groups of the obtained dendritic polyester (A-1) is 3 . It was 0 × 10 −5 equivalent / g.
分子末端カルボン酸基量測定は、中和滴定法によって行った。樹状ポリエステル(A−1)0.5gをo−クロロフェノール10mLに90℃で加熱しながら溶解させ、冷却した後、クロロホルム4mLを加えた。ブロモフェノールブルー−エタノール溶液(0.2重量%)を数滴加えた後、滴定試薬(0.04M水酸化カリウム−メタノール溶液)をビュレットを用いて滴下し、中和点に達するまでに滴下した滴定試薬量から樹状ポリエステル(A−1)の末端カルボン酸基量を計算した。The molecular terminal carboxylic acid group amount was measured by the neutralization titration method. 0.5 g of dendritic polyester (A-1) was dissolved in 10 mL of o-chlorophenol while heating at 90 ° C., cooled, and then 4 mL of chloroform was added. After adding a few drops of bromophenol blue-ethanol solution (0.2 wt%), a titration reagent (0.04M potassium hydroxide-methanol solution) was added dropwise using a burette and added until the neutralization point was reached. It was calculated terminal carboxylic acid group amount of dendritic polyester (a-1) from the titrant volume.
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